EP3900061B1 - Verbesserungen in bezug auf thermoelektrische materialien - Google Patents

Verbesserungen in bezug auf thermoelektrische materialien Download PDF

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Publication number
EP3900061B1
EP3900061B1 EP19828639.5A EP19828639A EP3900061B1 EP 3900061 B1 EP3900061 B1 EP 3900061B1 EP 19828639 A EP19828639 A EP 19828639A EP 3900061 B1 EP3900061 B1 EP 3900061B1
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Prior art keywords
lignin
thermoelectric
carbon nanotubes
fibres
thermoelectric material
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French (fr)
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EP3900061A1 (de
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Maurice COLLINS
Mario Culebras RUBIO
Juan Jose VILATELA
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University of Limerick
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Fundacion Imdea Materiales
University of Limerick
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/856—Thermoelectric active materials comprising organic compositions

Definitions

  • the present invention relates to a thermoelectric material, a thermoelectric element, a fabric, a thermoelectric device and a method of producing said thermoelectric material.
  • the invention relates to thermoelectric materials comprising carbon nanotube fibres impregnated with lignin which are suitable for use in wearable thermoelectric devices.
  • Thermoelectric materials are capable of directly converting heat into electricity. When a temperature gradient is applied to opposing parts or sides of the thermoelectric material, an electric voltage is induced by diffusion of charge carriers from one part or side of the thermoelectric material to the other. This property offers the potential to convert waste heat into usable electricity.
  • ZT figure of merit
  • PF power factor
  • PF ⁇ S 2 , the units of which are ⁇ W/K 2 m.
  • thermoelectric material is Bi 2 Te 3 , which has been used to manufacture thermoelectric devices known as Peltier modules.
  • Peltier modules thermoelectric devices
  • These known devices have several drawbacks, for example the toxicity of the materials, high costs of production and difficulties in producing large scale devices.
  • organic semiconductor materials such as conducting polymers or carbon-based nanocomposites may overcome some of these disadvantages.
  • thermoelectric efficiency achieved by some such materials is low which limits the usefulness of such materials, in part due to the large impedance of these materials.
  • thermoelectric material comprising a polymer interface layer and first and second layers disposed on different sides of the polymer interface layer comprising a plurality of aligned, wavy carbon nanotubes (CNTs).
  • thermoelectric conversion element which comprises a p-type thermoelectric conversion layer and an n-type thermoelectric conversion layer.
  • the p-type thermoelectric conversion layer comprises a nano-carbon material and an onium salt or an inorganic salt.
  • DALTON NIALL ET AL "Thermoelectric properties of electrospun carbon nanofibres derived from lignin",INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES, ELSEVIER BV, NL, vol. 121, 12 October 2018 (2018-10-12), pages 472-479, XP085535311,ISSN: 0141-8130 , discloses bio-based carbon nanofibres (CNFs) derived from mixtures of polyacrylonitrile and lignin using electrospinning.
  • CNFs carbon nanofibres
  • MILCZAREK GRZEGORZ ET AL Carbon nanotubes/kraft lignin composite: Characterization and charge storage properties
  • MATERIALS RESEARCH BULLETIN vol. 48, no. 10 , pages 4032-4038, XP028692728,ISSN: 0025-5408 , discloses a nanocomposite consisting of multi-walled carbon nanotubes and kraft lignin.
  • thermoelectric material that addresses at least one disadvantage of the prior art, whether identified here or elsewhere, or to provide an alternative to existing thermoelectric materials.
  • thermoelectric material which provides improved thermoelectric properties compared to known carbon nanomaterial-based materials.
  • thermoelectric material comprising carbon nanotube fibres impregnated with lignin.
  • the inventors have surprisingly found that the incorporation of lignin into carbon nanotubes may improve the thermoelectric properties of the carbon nanotubes.
  • the carbon nanotubes are carbon nanotube fibres.
  • the carbon nanotubes are suitably macroscopic fibres of carbon nanotubes.
  • the lignin is impregnated / incorporated into the carbon nanotubes. Therefore the lignin is incorporated into the carbon nanotubes (i.e. a network of carbon nanotubes) to form a nanocomposite material.
  • the thermoelectric material of this first aspect may be additionally or alternatively defined as carbon nanotube fibres impregnated with lignin or a composite of lignin and carbon nanotube fibres.
  • Lignin along with hemicellulose and cellulose, is one of the most abundant components of lignocellulosic biomass. Lignin is an amorphous material present in the cell walls of pith, roots, fruit, buds and bark and mainly comprises aromatic biopolymers. Lignin is produced as a very low value product form the pulp and paper industry.
  • the lignin acts as a dopant which may improve the thermoelectric properties of the carbon nanotubes and therefore form a composite material with electronic structure distinct from that of the constituent materials.
  • the aromatic and phenolic functionality in the lignin structure may provide good compatibility of the lignin with the carbon nanotubes and enable the lignin to undergo the charge transfer interactions which provide such a dopant effect to the thermoelectric material.
  • thermoelectric material of this first aspect may enable the production of relatively large scale thermoelectric devices due to the low cost of producing the thermoelectric material and the abundance of the raw materials, compared to the rare earth metals used in known thermoelectric devices, for example thermoelectric materials formed from Bi 2 Te 3 .
  • thermoelectric material of this first aspect may also enable the production of devices with augmented or improved mechanical properties, such as flexibility (in bending), tensile strength, ductility, toughness and the ability to be woven/knitted.
  • thermoelectric material of this first aspect may have mechanical properties which are suitable for the production of flexible and wearable thermoelectric devices.
  • the lignin used in the thermoelectric material of this first aspect may also provide the advantage of improving the environmental profile of thermoelectric materials due to the potentially more sustainable production of lignin compared to known dopants/thermoelectric material components.
  • carbon nanotube refers to a structure conceptually similar to that made by rolling up a sheet of graphene into a cylinder.
  • carbon nanotubes of different diameter and internal geometry can be formed.
  • Carbon nanotubes formed by rolling up of a single sheet forming the aforementioned cylinder are called “single-walled” carbon nanotubes (SWCNTs).
  • SWCNTs single-walled carbon nanotubes
  • MWCNTs multi-walled carbon nanotubes
  • Carbon nanotubes have high electrical conductivity and single-walled carbon nanotubes may generally have better thermoelectric properties than multi-walled carbon nanotubes.
  • the high cost of SWCNTs is problematic for the production of thermoelectric devices on a large scale.
  • MWCNTs are relatively inexpensive to produce compared to SWCNTs.
  • the carbon nanotubes of the thermoelectric material of this first aspect are suitably single-walled carbon nanotubes or multi-walled carbon nanotubes.
  • the carbon nanotubes of the thermoelectric material of this first aspect are multi-walled carbon nanotubes.
  • the inventors have found that the use of lignin with carbon nanotubes in a thermoelectric material may be particularly advantageous when the carbon nanotubes are multi-walled carbon nanotubes as the lignin may improve the generally less favourable thermoelectric properties of the multi-walled carbon nanotubes compared with single-walled carbon nanotubes.
  • the carbon nanotubes are multi-walled carbon nanotubes
  • the multi-walled carbon nanotubes suitably comprise from 2 to 5 graphitic layers.
  • the carbon nanotubes suitably have a high aspect ratio (length-to-diameter ratio), suitably an aspect ratio of between 10 and 10,000,000 to 1, suitably between 100 and 10,000,000 to 1.
  • the carbon nanotubes are also suitably highly graphitic.
  • thermoelectric material of this first aspect suitably comprises or consists of carbon nanotube-based fibres.
  • carbon nanotube-based fibres refers to a macroscopic array of agglomerated carbon nanotubes as defined above, where the fibre can be used as an individual filament, in a flat film or sheet, or as a woven or non-woven fabric.
  • the carbon nanotube-based fibers used in the present invention comprise pores or voids which are formed between the carbon nanotubes due to imperfect packing.
  • the carbon nanotube-based fibres used in the present invention are fibres having a specific surface area between 50 and 2000 cm 2 /g.
  • the carbon nanotubes are in the form of fibres having a specific surface area between 50 and 2000 cm 2 /g, suitably approximately 250 cm 2 /g.
  • the carbon nanotube-based fibres used in the present invention are fibres having a diameter between 0.1 and 1000 microns.
  • the carbon nanotubes are in the form of fibres having a diameter of 10 microns.
  • thermoelectric material of this first aspect for example lignin obtained from softwood, hardwood or grass/annual plants.
  • Suitable lignin can be obtained from these sources using various known processes, for example the Kraft, organosolve or soda processes.
  • more than one type and/or source of lignin is used to provide the lignin of the thermoelectric material.
  • the lignin is an organosolve lignin.
  • thermoelectric material comprises at least 5 wt% lignin, suitably at least 10 wt%, suitably at least 20 wt%.
  • thermoelectric material comprises up to 65 wt% lignin, suitably up to 60 wt%, suitably up to 55 wt%.
  • thermoelectric material comprises from 5 to 65 wt% lignin, suitably from 10 to 60 wt% lignin, suitably from 20 to 50 wt% lignin.
  • thermoelectric material comprises up to 10 wt% lignin, suitably up to 8 wt% lignin, suitably up to 6 wt% lignin.
  • thermoelectric material of this first aspect suitably comprises or consists of fibres of the carbon nanotubes impregnated and/or infiltrated with the lignin.
  • the fibres of carbon nanotubes comprise pores and/or voids into which the lignin is incorporated, to provide fibres of carbon nanotubes impregnated and/or infiltrated with lignin.
  • the lignin is present within pores of the carbon nanotube fibres, suitably between bundles of carbon nanotubes, wherein each bundle comprises around 2-10 carbon nanotubes.
  • the lignin and the carbon nanotubes are intimately mixed to coat the internal pores of the carbon nanotube fibres of the thermoelectric material, rather the lignin forming an outer layer around the carbon nanotube fibres, for example.
  • the carbon nanotube fibres may be referred to as "impregnated” and/or “infiltrated” with lignin.
  • thermoelectric material of this first aspect is suitably a yarn comprising a plurality of carbon nanotube fibres.
  • the carbon nanotube fibres in the yarn consist of an array of parallel carbon nanotube fibres bundled together, typically comprising from 10 to 100 carbon nanotube fibres.
  • Such yarns of carbon nanotube fibres can be produced, for example, by winding multiple carbon nanotube fibres onto the same spool and then physically bundling them together by manually rolling them off the spool sideways.
  • thermoelectric material of this first aspect is a yarn comprising at least 10 fibres of carbon nanotubes, suitably at least 100 fibres of the carbon nanotubes impregnated and/or infiltrated with the lignin.
  • thermoelectric element comprising a thermoelectric material according to the first aspect.
  • thermoelectric element may consist of a yarn of thermoelectric material as described in relation to the first aspect.
  • the thermoelectric element may be a fabric comprising yarns or fibres as described in relation to the first aspect.
  • thermoelectric element of this second aspect may be incorporated into a thermoelectric device, suitably a wearable thermoelectric device.
  • a fabric comprising a thermoelectric material according to the first aspect.
  • the fabric comprises a planar array of carbon nanotube fibres.
  • Such an array may be alternatively or additionally referred to as a "mat", as described in EP2631330B1 .
  • the terms "fabric” or “mat” in the context of the present invention may be used generally to refer to structures which are smaller in one dimension than in the other two dimensions. Fabrics or mats may be flat or curved in shape.
  • the fabric can be produced, for example, by winding multiple carbon nanotube fibres onto a spool and then physically consolidating the fabric by applying a mechanical force perpendicular to the plane of the fibres, that is, by pressing them down.
  • the fabric has a thickness of at least 0.01 ⁇ m, suitably at least 0.1 ⁇ m, suitably at least 1 ⁇ m.
  • the fabric has a thickness of up to 1,000 ⁇ m, suitably up to 100 ⁇ m, suitably up to 10 ⁇ m.
  • the fabric suitably has a thickness from 0.01 to 1,000 ⁇ m, suitably from 0.1 to 100 ⁇ m, suitably from 1 to 10 ⁇ m.
  • the fabric may be a woven or non-woven sheet, suitably comprising fibres of the carbon nanotubes impregnated and/or infiltrated with the lignin.
  • the fabric is a unidirectional non-woven sheet of fibres of the carbon nanotubes impregnated and/or infiltrated with the lignin, suitably having a thickness between 1 and 10 ⁇ m.
  • the fabric may be suitable for forming or incorporating into a wearable thermoelectric device.
  • thermoelectric device comprising a thermoelectric material according to the first aspect, a thermoelectric element according to the second aspect or a fabric according to the third aspect.
  • thermoelectric device is adapted to be arranged in use on a user's body and to generate electricity from heat from said body of said user.
  • thermoelectric device comprises an electrical circuit, suitably connected to opposite sides of the thermoelectric material.
  • thermoelectric device comprises a functional module which is connected to the electrical circuit in order to power the functional module.
  • the functional module may be a sensor, a screen or a communications device.
  • the thermoelectric device is a relatively low cost, scalable and flexible device.
  • the thermoelectric device has augmented or improved mechanical properties, such as flexibility (in bending), tensile strength, ductility, toughness and the ability to be woven/knitted, compared to known thermoelectric devices.
  • thermoelectric material comprising carbon nanotubes and lignin
  • thermoelectric material formed in the method of this fifth aspect is a thermoelectric material according to the first aspect, a thermoelectric element according to the second aspect or a fabric according to the third aspect.
  • step a) is carried out before step b).
  • step a) involves producing the fibres of carbon nanotubes by chemical vapour deposition.
  • step a) involves producing the fibres of carbon nanotubes by direct spinning from a gas phase.
  • the fibres of carbon nanotubes may be synthesized by a direct spinning method which involves the continuous withdrawal of a carbon nanotube aerogel directly from a gas-phase during growth of the carbon nanotubes by floating catalyst chemical vapor deposition.
  • a direct spinning method which involves the continuous withdrawal of a carbon nanotube aerogel directly from a gas-phase during growth of the carbon nanotubes by floating catalyst chemical vapor deposition.
  • Such a reaction may be carried out in hydrogen atmosphere at 1,250 °C, using a S/C ratio to produce fibres predominantly made up of muti-walled carbon nanotubes.
  • a carbon nanotube fabric may be prepared by winding multiple fibres of carbon nanotubes onto a rotating bobbin under transverse motion. The resulting porous fabric may be consolidated by densification, for example with acetone, and dried at room temperature.
  • step b) involves treating the fibres of carbon nanotubes with a solution comprising the lignin and a solvent.
  • the solvent is an organic solvent, for example tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • the solvent is a polar aprotic organic solvent.
  • the solvent may be selected from dimethylformamide (DMF), dimethylsufoxide (DMSO), acetone and THF.
  • Step b) may be carried out as a separate step in a batch-wise process. Alternatively, step b) may be carried out in-line immediately after step a) has been carried out as the fibres of carbon nanotubes are produced.
  • Step b) may be carried out by a plurality of fibre impregnation methods, such as bath immersion, spraying and wet-rolling, amongst others.
  • the inventors have found that the method of this fifth aspect can be used to incorporate lignin from different sources into the carbon nanotubes.
  • This treatment of the carbon nanotube fibres favours infiltration and interaction of the lignin with the carbon nanotube fibres leading to enhanced thermoelectric properties of the composite material produced.
  • a non-woven unidirectional fabric was produced by winding fibres of carbon nanotubes onto a bobbin and densifying the material with a solvent.
  • such a fabric was produced from carbon nanotube fibres that were directly collected from the gas-phase during their synthesis by chemical vapour deposition, as described in EP2615193B1 , EP2631330B1 and EP2631331A1 .
  • this method of preparing the carbon nanotube fibres involves the production of a carbon nanotube agglomerate, comprising the steps of: passing a flow of one or more gaseous reactants into a reactor; reacting the one or more gaseous reactants within a reaction zone of the reactor to form an aerogel; agglomerating the aerogel into an agglomerate; and applying a force to the agglomerate to displace it continuously away from the reaction zone.
  • porous nature of fibres of carbon nanotubes formed from said methods allows the infiltration of lignin into the fabric. Infiltration with lignin can be carried out in-line as the fibre is produced and wound as a fabric, or in a subsequent step.
  • the carbon nanotube fibre fabrics were immersed in a 5 wt% solution of lignin (organosolv hardwood provided by Thecnaro, Germany) in THF for 5 minutes.
  • the carbon nanotube fibre fabric was then dried at 70 °C for 1 hour.
  • Carbon nanotube fibre yarns were impregnated with lignin using the same methods as described above.
  • Table 1 shows the different concentrations of lignin/THF solutions which were used and the wt% of lignin in the CNT/lignin yarns produced, measured by calculating the difference between the weight of the samples before and after impregnation with lignin and drying.
  • Table 1 - Yarns Yarn sample no. Lignin concentration in THF Solution Amount of lignin in yarns wt. % wt.% 1 1.00% 13% 2 2.50% 23% 3 5.00% 34% 4 10.00% 53% 5 20.00% 56%
  • Figure 1 shows scanning electron microscope (SEM) images of the fabric (a) before and (b) after lignin infusion. These SEM images show the morphology of the fabric before and after lignin infusion. A comparison of the SEM images indicates how lignin has filled the gaps/voids between the carbon nanotube fibres in the fabric.
  • SEM scanning electron microscope
  • the electrical conductivity of the fabric prepared as described above was obtained using the van der Pauw method. This method can be utilized to determine the conductivity of thin films wherein the distance between contacts is much larger than the sample thickness. Four contacts to the fabric were used in this method to eliminate the effect of the contact resistance.
  • the sample was placed between two Peltier modules powered by a power supply.
  • the temperature was measured by k-type thermocouples while the voltage was recorded using a Keithley 2000 multimeter.
  • Table 2 shows the thermoelectric properties of the fabric before ("Comp.” denotes comparative sample) and after lignin infusion (samples 2 to 5).
  • Table 3 shows the same data for yarn samples 1-5 and the lignin-free "comparative" sample.
  • the results in Table 1 indicate that after lignin infusion the power factor increases significantly, mainly due to the increase in the Seebeck coefficient.
  • Table 2 Thermoelectric parameters of the fabric samples. Fabric sample no. Lignin conc.
  • Figures 2 and 3 show voltage generated as a function of the temperature difference of the "pristine” and “impregnated” fabrics and yarns respectively.
  • lignin both of the parameters - electrical conductivity and Seebeck coefficient - increase. Therefore the thermoelectric efficiency given by the PF is higher compared to the comparative sample which comprises carbon nanotubes with no lignin impregnation.
  • These results show a significant increase of approximately an order of magnitude in the PF with the lignin impregnated samples 2-5.
  • thermoelectric materials and thermoelectric devices comprising such lignin impregnated carbon nanotube fibres may generate electricity more efficiently that known thermoelectric materials and devices, particularly compared to known multi-walled carbon nanotube thermoelectric materials and devices.
  • FIG 4 shows a schematic representation of a thermoelectric device (100) according to the fourth aspect of the present invention.
  • the thermoelectric device (100) comprises a fabric (110) according to the third aspect of the present invention and a nickel wire (120) wound through the fabric (110).
  • the fabric (110) comprises carbon nanotube fibres and lignin, and was prepared as described above.
  • the thermoelectric device (100) is a wearable thermoelectric device for body heat recovery. The temperature difference between the user's skin (20) and ambient air (30) (outside of the user's skin (20) and the thermoelectric device (100)) produces a temperature difference between the skin side (130) and the air side (140) of the thermoelectric device (100).
  • thermoelectric device (100) can generate useful electricity from the user's body heat which would otherwise be lost to the atmosphere.
  • the thermoelectric device (100) may be able to do this more effectively than if the lignin was not present in the fabric.
  • FIG 5 shows the test set-up (40) used to determine the electrical conductivity of the yarn samples (150).
  • Four electrical contacts (11) are made in the sample yarn (150) with silver paint.
  • the electric current (A) is applied between end contacts (12) and the voltage (V) is measured between the internal contacts (13).
  • FIG. 6 shows a schematic of a thermoelectric device (200) comprising twenty pieces of carbon nanotube fibre yarn impregnated with lignin (150).
  • the device was prepared by first preparing twenty 5 mm long yarns impregnated with lignin (from a 2.5 wt% lignin solution in THF), which may be considered "thermoelectric elements", and grouping these into four sets of five carbon nanotube fibre yarns (250). Each of these sets were bound together with cooper wire (220), with the top of one yarn being tied to the bottom of the next.
  • a schematic of such a group of carbon nanotube fibre yarns is shown in Figure 6(a) .
  • the copper wire was secured to the yarns with silver paint to ensure good contact.
  • FIG. 6(b) demonstrates the power output of the thermoelectric device (200) in use, showing the evolution of power as a function of the electrical current generated at temperature gradients of 30 °K and 20 °K.
  • the device (200) showed a maximum power value of around 3.5 ⁇ W. This is a surprisingly high power output for such a thermoelectric device having twenty thermoelectric elements.
  • Known devices having a similar number of thermoelectric elements have been reported to produce power outputs in the nW range, therefore orders of magnitude lower than the power output which may be provided by the thermoelectric device of the present invention.
  • the present invention provides a thermoelectric material comprising carbon nanotube fibres impregnated with lignin.
  • the carbon nanotubes are present as fibres and the lignin is present in pores and/or voids in the carbon nanotube fibres.
  • the lignin may act as a dopant to increase the thermoelectric efficiency of the carbon nanotubes, multi-walled carbon nanotubes in particular.
  • a method of forming a thermoelectric material involving impregnating fibres of carbon nanotubes with lignin, is also provided.
  • a thermoelectric element, a fabric and a thermoelectric device comprising the thermoelectric material are also provided. The thermoelectric material may be particularly useful for the production of wearable thermoelectric devices.
  • compositions consisting essentially of a set of components will comprise less than 5% by weight, typically less than 3% by weight, more typically less than 1 % by weight of non-specified components.
  • thermoelectric material comprises at least 2 wt% lignin
  • 2 wt% of the thermoelectric material is provided by lignin.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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Claims (15)

  1. Thermoelektrisches Material, dadurch gekennzeichnet, dass es Fasern aus Kohlenstoff-Nanoröhrchen umfasst, die mit Lignin imprägniert sind.
  2. Thermoelektrisches Material nach Anspruch 1, wobei die Kohlenstoff-Nanoröhrchen mehrwandige Kohlenstoff-Nanoröhrchen sind.
  3. Thermoelektrisches Material nach Anspruch 1 oder 2, wobei die Fasern aus Kohlenstoff-Nanoröhrchen eine spezifische Oberfläche zwischen 50 und 2000 cm3/g aufweisen.
  4. Thermoelektrisches Material nach einem der vorhergehenden Ansprüche, wobei das Lignin ein in organischen Lösemitteln lösliches Lignin ist.
  5. Thermoelektrisches Material nach einem der vorhergehenden Ansprüche, mindestens 2 Masse-% Lignin enthaltend.
  6. Thermoelektrisches Material nach einem der vorhergehenden Ansprüche, mindestens 10 Masse-% Lignin enthaltend.
  7. Thermoelektrisches Material nach einem der vorhergehenden Ansprüche, wobei das thermoelektrische Material ein Garn ist, das die Fasern aus den Kohlenstoff-Nanoröhrchen umfasst.
  8. Thermoelektrisches Element, ein thermoelektrisches Material nach einem der vorhergehenden Ansprüche umfassend.
  9. Gewebter Stoff, ein thermoelektrisches Material nach einem der Ansprüche 1 bis 7 umfassend.
  10. Thermoelektrische Vorrichtung, ein thermoelektrisches Material nach einem der Ansprüche 1 bis 7, ein thermoelektrisches Element nach Anspruch 8 oder einen gewebten Stoff nach Anspruch 9 umfassend.
  11. Thermoelektrische Vorrichtung nach Anspruch 10, wobei die thermoelektrische Vorrichtung eingerichtet ist, um in Benutzung auf einem Körper des Benutzers angeordnet zu sein und Elektrizität aus Wärme von dem Körper des Benutzers zu erzeugen.
  12. Verfahren zur Herstellung eines thermoelektrischen Materials, das Kohlenstoff-Nanoröhrchen und Lignin enthält, das Verfahren dadurch gekennzeichnet, dass es die folgenden Schritte umfasst:
    a) Bereitstellen von Fasern aus Kohlenstoff-Nanoröhrchen;
    b) Imprägnieren der Fasern aus Kohlenstoff-Nanoröhrchen mit Lignin.
  13. Verfahren nach Anspruch 12, wobei Schritt a) Produzieren der Fasern aus Kohlenstoff-Nanoröhrchen durch chemische Bedampfung einbezieht.
  14. Verfahren nach Anspruch 12 oder 13, wobei Schritt a) Produzieren der Fasern aus Kohlenstoff-Nanoröhrchen durch Direktspinnen aus einer Gasphase einbezieht.
  15. Verfahren nach einem der Ansprüche 12 bis 14, wobei Schritt b) Behandeln der Fasern aus Kohlenstoff-Nanoröhrchen mit einer Lösung einbezieht, die das Lignin und ein Lösemittel enthält.
EP19828639.5A 2018-12-18 2019-12-13 Verbesserungen in bezug auf thermoelektrische materialien Active EP3900061B1 (de)

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GB1820651.6A GB2579864A (en) 2018-12-18 2018-12-18 Improvements relating to thermoelectric materials
PCT/EP2019/085102 WO2020126912A1 (en) 2018-12-18 2019-12-13 Improvements relating to thermoelectric materials

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GB0316367D0 (en) 2003-07-11 2003-08-13 Univ Cambridge Tech Production of agglomerates from gas phase
EP2536780A4 (de) * 2010-02-15 2013-11-13 Lignol Innovations Ltd Kohlefaserzusammensetzungen mit ligninderivaten
US20110285049A1 (en) * 2010-05-19 2011-11-24 Baker Frederick S Carbon nanotube (cnt)-enhanced precursor for carbon fiber production and method of making a cnt-enhanced continuous lignin fiber
WO2016090363A1 (en) 2014-12-05 2016-06-09 Stc.Unm Method of dispersing nanoparticles in different mediums & methods to achieve superior thermoelectric performances in carbon nanotube polymer systems
EP3322669A4 (de) * 2015-07-13 2019-03-20 Alliance for Sustainable Energy, LLC Verfahren zur herstellung von einwandigen kohlenstoffnanoröhrennetzwerken
JP2019502839A (ja) * 2016-01-26 2019-01-31 フラウンホーファー・ゲゼルシャフト・ツール・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファウ 炭素繊維用の前駆物質としてのリグニン含有繊維を製造するための湿式紡糸方法
WO2018012377A1 (ja) 2016-07-11 2018-01-18 富士フイルム株式会社 熱電変換素子
JP2018067608A (ja) * 2016-10-18 2018-04-26 日本精工株式会社 熱電変換素子
FR3058166B1 (fr) * 2016-10-28 2018-11-23 Arkema France Procede de fabrication de fibres de carbone a partir de precurseurs biosources et fibres de carbone obtenues

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US20220052246A1 (en) 2022-02-17
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GB2579864A (en) 2020-07-08
WO2020126912A1 (en) 2020-06-25

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